Coloration of materials



- Patented Sept 27t 1938 UNITED STATES IPATENTQOFFICE coLona'rIoN or MATERIALS Henry Dreyius, mason, England No Application September 20, 1935,

Serial No. 41,419. In Great Britain ber 28, 1934 v 10 Claims.

This invention relates to the coloration of materials made 01' or containing synthetic resins. At the present'time synthetic resins find extensive and increasing employment in numerous industries. Amongst the many industries in which these bodies are employed there may be mentioned the plastic industry and the textile industryr During recent years textile materials impregnated withor containing synthetic resins have come into prominence. Such textiles are not so readily colored by the dyestuilfs customarily em-' ployed icr dyeing the materials in the absence of the synthetic resin. I have now found that 15 such materials maybe colored with unsulphonated coloring matters or with sulphonated coloring matters in which the sulpho group represents a relatively small part of the whole dyestufl molecolored by the above means, but also other materials made or or containing synthetic resins and having at least one dimension small in relation 5 to another, ior example films or filaments.

Various coloring matters may be employed for coloring textile materials impregnated with or containing synthetic resins or other synthetic resin materials in accordance with the present 40 invention. Thus there may be employed unsuiphonated or other relatively insoluble derivatives of the "am" class, e. g. unsulphonated azo dyestuiis obtainable from amino naphthols or their nuclear substitution products and containing the 5 azo group linkedto the naphthalene nucleus in a position ortho or peri to an auxochromic group; unsulphonated azo dyestuil's obtainable from naphthylene diamines; unsulphonated azo dyestufls containing an anthraquinonenucleuae; g. 50 2-methyl-anthraquinone-l azo-dimethyl-metaamino-phenol; insoluble or relatively insoluble pyrazolone derivatives, for example unsulphonated azo derivatives of pyrazolone compounds, such for example as those obtained by coupling l-phen- 65 yl-S-methyl-B-pyrazolone, or 1.3-dimethyl-5- pyrazolone with diazotized amino compounds, e. g. diuo compounds from aniline. para-anisidine, f"para-aminobenzene-azo-dimethylaniline, paradimethyl-amino-aniline or para-amino-phenol;

60 unsulphonated. azo derivatives of 2:4-dinitroY6- Septemalkoxy or alkyl anilines obtainable by diazotizing the aniline derivative and coupling with coupling components of the naphthalene or other suitable series; unsulphonated coloring matters or compounds of the stilbene group, for example 5 stilbene disazobisphenol, stiibene disazobis-mtoluidine, stilbene disazobis-a-naphthylamine,

amino-stilbene-azo-meta-phenylenediamine, or

aminostilbene-azo-metatoluidine; unreduced indophenols (aryl or substituted aryl benzoor 10 naphtho-quinone-mono-imidesJ or insoluble or relatively insoluble coloring matters of. polyaryl-' methane, oxazine, azine, thiazine and thiazole series, or unreduced basic derivatives of the anthraquinone series, e. g. rosaniline base or its alkylated or arylated derivatives, pararosaniline base, malachite green base, sairanine base. aminoand aminohydroxmanthraquinones or their derivatives such as 1-paratolylamino-4-hy droxy-anthraquinone, 1-paratolylamino-4-meth- 2 ylamino-anthraquinone, and especially anthraquinone derivatives substituted in three alpha positions by a hydroxyl group, an arylamino group and an amino group respectively; or insoluble or relatively insoluble acidyl derivatives of amino anthraquinones or of substituted amino anthraquinones, containing one or more aliphatic acidylamino groups, e. g. acetyl-,'propionyl-, only], or sucoinyl -amino "groups with or without other substituent groups such as amino. hydroxy, chlor and the like, for example 1-acetyl-aminoanthraquinone or l-acetylamino- 4-oxy, -4-methoxy, -4-,amino, -4-methyla'mino or -4:5:8-triamino anthraquino'nes and soforth;

hetero-nuclear di-a-hydroxy by an arylamino group and in the other a-DOSI- tion by an amino or a non-.aromatically substituted amino group. e. g. 4-amino-8-phenylamino-lzb-dihydroxy'anthraquinone or 4-amino-5- 40 kyl, alkoxy, hydroxy, halogen or amino derivaiii)- tives; 4-nitro-diphenylamine, or its alkyl, a1- koxy or-halogen derivatives; 2-nitro-diphenylamine and its halogen, alkyl and alkoxy-amino or acidyl-amino derivatives, e. g. 2-nitro-4-chior- 4'-methyl-diphenylamine, 2 nitro 4: chlor-4'- 65 1 ethoxy-diphenylamine; nitro amino diaryl compounds, for example 8 -nitro-4-amino-diphenyl, 3 nitro-4 amino-'4'-acetylamino-dipheny1,1 or other nitro-amino-diaryl compounds and compounds obtainable by diazotizing these bodies and anthraquinones 35-' 'substituted in one ofthe remaining a-positions coupling with suitable coupling components; the nitrogenous bodies obtainable by introducing nitrogen into naphthazarine' or nuclear substitution products thereof with the aid oi. ammonia; N- (nitro-aryl)-ar-tetrahydro-s-or p-naphthylamines; or there may be employed unsuiphonated compounds obtainable by the introduction of one or more p-keto-acidyl groups into aminov ous dispersions or in more or less colloidal form as obtainable for instance with the aid of one or. more suitable dispersing agents. For examples of dispersing agents suitable for use in the production of dispersions of dyestuifs for use in accordance with the present invention reference may be made to U. S. Patent Nos. 1,618,413, 1,618,414, 1,694,413, 1,690,481, 1,803,008, 1,840,572, 1,716,721, 1,928,647, 1,959,352, and U.

S. application S. N02 493,224 filed 3rd November If desired the dispersing agent may be used in conjunction with an organic solvent for the coloring matter, particularly a substantially water-in soluble organic solvent. Such solvents are hereinafter referred to as auxiliary solvents". This process of using auxiliary solvents is of especial use in the dispersion of difllcultly dispersible coloring matters or compounds.

Examples of auxiliary solvents which may employed include the following:-

(a) Aliphatic hydrocarbons, e. g. hydrocarbons from petroleum; (b) Aromatic and hydroaromatic hydrocarbons,-

e. g. benzene, toluene, xylene, eymene, cyclohexane, t'etrahydro-naphthalene and decahydronaphthalene; (c) Terpenes, e. g. turpentine thereof; (d) Halogenated hydrocarbons, e. g. halogenated aliphatic hydrocarbons such as tetrachlorethane, trichlorethylene, and carbon tetrachloride, and halogenated aromatic hydrocarbons such as chlorbenzene; i (e) Alcohols or phenols, e. g. butyl alcohol, 'amyl alcohol, cyclohexanol, methyl cyclohexanols,

' phenol and cresols; (I) Esters, e. g.'butyl acetate and my] acetate.

Mixtures oi. auxiliary solvents may be used if desired, for example commercial liquids such as fractions of petroleum etc. It will be appreci ated, of course; that the auxiliary solvent should be chosen with due attention to the solubility characteristics of the particular synthetic resin to be treated, one being chosen that will not deleteriously affect the resin. At the same time, a suitable choice of auxiliary solvent may further lead to better penetration of the dyestuif into the material treated. Thus the penetration of dyestuil's, azo components and the like into synthetic resin materialsmay be facilitated by means 01 swelling agents for thesynthetic resin,

- and some of the above auxiliary solvents may act as swelling agents for the resin and so aid penetration of the dyestuif into the material.

or constituents Q pounds, eg. aniline, thereon.

Again the dyestuii preparation employed in the coloration oi synthetic resin materials may 7 contain any other desired ingredients, e. g. swelling agents other than and in addition to any 01' the bodies listed above. As swelling agents there 'may be employed solutions or dispersions oiv sub-. stances having a solvent action on the resin.

It will readily be appreciated that the swelling agents must be chosen with reference tothe properties of the synthetic resin in the'material. Thus phenol-aldehyde resins in the A stage of condensation are soluble in a large number of organic solvents by which they are merely swollen when in the B stage of condensation, whilst in the 0 stage they are unaflected' by those solvents. Examples of swelling agents which may be employed in the treatment of phenol-aldehyde resins when in the B stage of condensation are alcohols, e. g. ethyl butyl or amyl alcohol, ketones,

esters or other organic compounds, for example acetone, methyl ethyl ketone or ethyl or butyl acetate. For polyvinyl resins hot water may have a suflicient swelling effect. Phenols and phenolic compounds may also'be employed as swelling agents for some synthetic resins, while,.

as has been indicated, many of the auxiliary solvents mentioned in connection with the produc-- tion 01' dispersions may exercise on resinous materials.

When dyeings or colorings are to be produced by the azoic or development process the insoluble or relatively insoluble component or components (whether-base or developer or both) may be applied ineither order or simultaneously to the materials and diazotization and development eiiected, or the diazo compound itself may be 'applied to the material before or after application a swelling action of the coupling components and the color developed on the materials. The relatively insoiuble components are conveniently 'applied in the form of dispersions prepared, for example with the aid of any 01' the dispersing. agents and/or protective colloids and/or auxiliary solvents v mentioned above. "The invention further includes theproductionof black and other colorations on materials made of or containing synthetic resins by the oxidation of aromatic compounds, particularly aromatic amino com- For printing or stenciiling synthetic ma- .terials, an aqueous or other dispersion of one or more coloring matters or compounds may. be

thickened by the use of such substances as starches. flour, gums and the nice and applied in the usual manner. Where the dyestufls are soluble in water they mayiurther be applied from aqueous solutions. Dyeing, printing or other treatments in accordance with the present invention may be followed by steaming, ageing or any other after-treatment that may be desirable.

While the invention is broadly applicable to the coloration of any materials made oi! or containing synthetic-resins, such ior example as films or filaments. e. g. filaments or a polymerized vinyl compound such as a polymerized vinylv acetate. it is, as has been indicated, of especial importance in connection with the coloration of textile materiais coated or impregnated with synthetic. resins, e. g. textile materials to which an anti-- crease finish has been imparted by impregnation with a synthetic resin. The textilebase may be colored in the same shade as is the resin impregnant or in a different shade. Cross dyed effects may be obtained on knitted, woven, or

Examples. of synthetic resins which may be colored in accordance with the present invention are the-phenol-aldehyde resins, diphenylol-propane-formaldehyde resins, diphenylol-propanefurfural resins, and diphenylol cyclo paraifin-aldehyde resins, the condensationproducts of urea or thiourea with aldehydes with or without phe nols, aromatic sulphonamide-aldehyde resins, the polyhydric alcohol-polybasic acid resins such for example as the glycerol-phthalic anhydride resins, synthetic resins obtainable from Phenols,

cresols, xylenols and other phenolic bodies by condensation with chlor-acetone, furfural, allyl alcohol and other allyl compounds, sulphur chlorides, acetaldehyde, crotoneldehyde, betobutanol and chloral, the resinous products obtainable from phenolic bodies includingphenol itself, the cresols, the xylenols, resorcinol'and pyrocatechin' and acetone or other aliphatic ketones or cycloparaflgn ketones,hydroxybenaophenone-aldehyderesins', e. g. 2:4- or 4:4'-dihydroxy benzophenone-formaldehyde resins and themethyl dihydroxy benzophenone-aldehyde resins, and the resins or other products obtainable by the P lymerization of vinyl compounds, acrylic compounds, and other unsaturated compounds or the condensation products of. vinyl compounds with aldehydes and the like. The invention finds its chief use where the synthetic resins are not in a state of complete insolubilit'y and infusibility.

The invention is illustrated but not limited y the following examples, the proportions being expressed as parts by-weight:--

' Example 1 To dye a cotton fabric which has been impregnated with about 20% of its weight of synthetic resin by mercerizing with caustic soda solution,

washing. impregnating while still wet with a solution made by boiling 50 parts of 40% formaldehyde with 50' parts of phenol and a littlepotas slum carbonate for 5 minutes, squeezing to remove. excess solution, and drying for 1-3 minutes at 170 C.

1 part of i:4-di-(methylamino)-anthraquinone is pasted with parts of xylene and heated to about 70 .C. The mixture is then'pouredinto parts of Turkey red .oil, heated with em. and the whole poured into 8000 parts of soft water'at about C. '75 parts of the-resindm- M -ammonium .1-

pregnated cotton fabric is dyed in this bath-at 90-100 0. for about 1-155 hours. The material isthenrinsedanddried. f

2 v 7 I; I Todyeavlsoosefabrictowhichanantim finishhasbeenimpartedbyimpregnating witha mixture of 10 parts of 40% formaldehyde, 5

partsofureazpartsofboricaoidandflpartsofwater, followed by to remove liquor much in excessof the weight of the fabric .and drying at about 130 for 20-30 minutes.

wnirro m or xylene dyebath with-15 parts of ample 1 is dyed for 1 hour in. adyebath consisting of 2 parts of 1-amino-4-hydroxy-anthaqui- -".1

; rial fimpreenatedwith a urea formaldehyde resin,

"3000 parts of 7 water I -in Example 1. The fabric is dyed inthis dyebathv for about 1 1 hours at-80-90 C. It is=-. then rinsed and dried and finished as desired. .j Examples 100 parts of cotton fabric impregnated with {u phenol-formaldehyde resin as described in Ex-I 10 none dissolved in. 8000 parts of carbon tetrachloride, the dyeing temperature being about C. When dyeing is complete the material is centrifuged and dried,

What I claim and desire Patent-is:--- v 1. Process for, the coloration, of textile material or film comprising a synthetic resin, which comprises applying thereto an aqueous dispersion of a water-insoluble dye compound containing at the most onesulphonicgroup. 2. Process for the coloration of textile material or film comprising a syntheticresin, which com- A prises incorporating therein awater-insolubledye. component containing at the most one sulphon'ic group by treatment with an aqueous dispersion of the dye component, and thereafter converting said dye "component into dyestufi on the material. 3. Process for the coloration of textile material v or film comprising a synthetic resin, which com- 30 prises applying thereto an aqueous dispersion of a water-insoluble unsulphonated dyestuif.

Process for the coloration of textile material or film comprising a synthetic resin, which com-- prises incorporating therein a water-insoluble unsulphonated dye component by treatment with an aqueous dispersion of. the dye component, and thereafter converting said dye component into dyestuff on the material.

5. Process for the'colo to secure by Letters V ation of textile material 4 impregnated with a syn hetic resin, which ooman -unsulphonated water-insoluble dyestuif.

6. Process forthe coloration of textile material impregnated with a synthetic resin, which comprises applying theretosn aqueous liquid having dispersed therein a substantially water-in- 4 soluble dye and a liquid'having a softening action on the synthetic resin.

fl. Processfor the coloration of textile material impregnated with a synthetic resin, which comprises incorporating therein a water insoluble un-. sulphonated dye component by treatment with an aqueous dispersion thereof and thereafter conq vertingthe dye component into a dye.

8. Process for the coloration of textile material impregnated with a synthetic resin, which comprises incorporating therein a water-insoluble diasotizable amine by treatment with'an aqueous dispersion of the diasotizable amine, and thereafter diazotising the amine and coupli s with an aao dye coupling component.

, 0. Process for the coloration of textile impregnated with a phenol-formaldehyde resin, which comprises applying thereto an unsulphonated water-insoluble dyestuff by treatment with an aqueous dispersion thereof.

10. Process for the coloration of a textile matewhieh: comprises applying thereto an unsuii tcd water-insoluble dyestuif-lry treatment with an aqueous dispersion thereof.

in t he manner I 

